CN115124765B - Flame-retardant heat-conducting agent for general rubber, and preparation method and application thereof - Google Patents
Flame-retardant heat-conducting agent for general rubber, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of flame-retardant heat conduction, and particularly relates to a flame-retardant heat-conducting agent for general rubber, which is prepared by preparing sea urchin-shaped ferroferric oxide by a hydrothermal method, grafting and modifying the surface of the sea urchin-shaped ferroferric oxide by KH-550, and finally reacting the sea urchin-shaped ferroferric oxide with pyrophosphoric acid. The invention also relates to a preparation method of the flame-retardant heat-conducting agent and a method for using the flame-retardant heat-conducting agent in flame-retardant heat-conducting general rubber. By adopting the scheme, the rubber material flame-retardant heat-conducting agent is added into the rubber material as a synergistic flame retardant of the aluminum diethylphosphinate. The flame-retardant heat-conducting agent can have a good synergistic effect with diethyl aluminum phosphinate in the combustion process, has good char forming capability, can isolate oxygen and heat, integrates condensed phase flame retardance and gas phase flame retardance, and greatly improves the flame retardant property of the rubber composite material. Meanwhile, the heat-conducting performance of the rubber composite material is improved by adding the flame-retardant heat-conducting agent.
Description
Technical Field
The invention belongs to the field of flame-retardant heat conduction, and particularly relates to a flame-retardant heat-conducting agent for general rubber, and a preparation method and application thereof.
Background
Rubbers such as Natural Rubber (NR), styrene Butadiene Rubber (SBR), and Butadiene Rubber (BR) are all general-purpose rubbers. General purpose rubbers are widely used in tires, cables, automobile parts, conveyor belts, and other products. However, general rubber materials are extremely flammable, and the limiting oxygen index of most general rubbers does not exceed 20%. And the general rubber materials are poor conductors of heat, which limits their range of application.
The phosphorus flame retardant is considered to be a high-efficiency flame retardant and has small harm to the environment. Among the phosphorus flame retardants, aluminum Diethylphosphinate (ADP) is a halogen-free flame retardant having excellent flame retardancy. Upon combustion of the polymer, ADP can release a phosphorus-containing compound that can be converted to a phosphorus-containing radical quencher, thereby enhancing the flame retardant properties of the polymer. However, a large amount of additive is needed to achieve a certain flame retardant effect, which often causes the mechanical properties of the rubber compound to be poor, so that the rubber compound needs to be synergistic with other flame retardants.
The silane coupling agent modified flame retardant can effectively improve the binding property between the flame retardant and the composite material. And the synergistic effect between the flame retardants is enhanced, and the heat-conducting property of the composite material is effectively improved.
The ferroferric oxide can be controlled to generate different micro-morphologies by different methods. By controlling the sea urchin-shaped ferroferric oxide to be added into the rubber material, a three-dimensional heat conduction path can be formed, and the heat conduction performance of the rubber composite material is improved. In addition, ferroferric oxide subjected to pyrophosphoric acid surface modification is added into the general rubber material, so that the ferroferric oxide has a good synergistic effect with diethyl aluminum hypophosphite, and the flame retardant property of the rubber composite material is improved.
Disclosure of Invention
The invention aims to provide a flame-retardant heat-conducting agent for general rubber with excellent flame-retardant heat-conducting performance.
In order to realize the purpose, the invention adopts the technical scheme that: a flame-retardant heat-conducting agent for general rubber is characterized in that: the flame-retardant heat-conducting agent is prepared by firstly preparing sea urchin-shaped ferroferric oxide by a hydrothermal method, then performing graft modification on the surface of the sea urchin-shaped ferroferric oxide by KH-550, and finally reacting the sea urchin-shaped ferroferric oxide with pyrophosphoric acid.
The invention also aims to provide a preparation method of the flame-retardant heat-conducting agent for the general rubber, which comprises the following steps:
(a) Dispersing ferrous salt in a glycerol-water solution, and reacting for 12-24h in a hydrothermal reaction kettle at 110-150 ℃ to obtain sea urchin-shaped FeOOH;
(b) Dispersing sea urchin-shaped FeOOH and glucose in water, reacting for 12-24h in a hydrothermal reaction kettle at 160-200 ℃ to obtain reaction precipitate, and calcining the precipitate to obtain sea urchin-shaped ferroferric oxide;
(c) Dispersing sea urchin-shaped ferroferric oxide in ethanol, adding KH-550 at 60-80 ℃ for reaction for 3-5h, then adding pyrophosphoric acid for reaction for 1-3h, filtering, washing, precipitating and drying to obtain the general flame-retardant heat-conducting agent for rubber.
Specifically, in the step (a), the volume ratio of glycerol to water in the glycerol-water solution is 1:30-50. The ferrous salt is ferrous sulfate; the concentration of the ferrous salt is 0.025-0.035M.
In the step (b), the mass ratio of the sea urchin-shaped FeOOH to the glucose is (0.5-1.5 g): 1g.
In the step (b), the calcination is to react the precipitate with N 2 Calcining for 2-4h at 700-900 ℃ in the atmosphere to obtain the sea urchin-shaped ferroferric oxide.
In the step (c), the mass molar ratio of the sea urchin-shaped ferroferric oxide to the KH550 to the pyrophosphoric acid is 10g, i.e., 0.05 to 0.1mol and 0.025 to 0.05 mol.
The invention also provides a preparation method of the flame-retardant heat-conducting general rubber, which is prepared by mixing the flame-retardant heat-conducting agent or the flame-retardant heat-conducting agent prepared by the method and other raw materials in parts by mass as follows: 100 parts of general rubber, 5 parts of ZnO, 2 parts of stearic acid, 1.5-2.5 parts of vulcanization accelerator NS, 1.5-2.5 parts of anti-aging agent RD, 30-50 parts of carbon black, 1.5-2.5 parts of sulfur, 15-20 parts of diethyl aluminum phosphinate and 5-15 parts of flame-retardant heat-conducting agent.
The general rubber is at least one of butadiene rubber, styrene butadiene rubber and natural rubber. The mixing method of the general rubber comprises the following steps: adding general rubber, zinc oxide, stearic acid, an anti-aging agent, an accelerator, carbon black, diethyl aluminum hypophosphite, a flame-retardant heat-conducting agent and sulfur into an internal mixer in sequence; after mixing uniformly, pressing into tablets in an open mill, and vulcanizing by a flat vulcanizing machine, wherein the vulcanizing pressure is 5MPa, the vulcanizing time is 10-30min, and the vulcanizing temperature is 150-170 ℃.
By adopting the scheme, the rubber material flame-retardant heat-conducting agent is added into the rubber material as a synergistic flame retardant of aluminum diethylphosphinate. The flame-retardant heat-conducting agent can have a good synergistic effect with diethyl aluminum phosphinate in the combustion process, has good char forming capability, can isolate oxygen and heat, integrates condensed phase flame retardance and gas phase flame retardance, and greatly improves the flame retardant property of the rubber composite material. Meanwhile, the flame-retardant heat-conducting agent is added, so that the heat-conducting property of the rubber composite material is improved.
Drawings
FIG. 1 is a graph of the heat release rate for samples one, two, and three of example 1;
FIG. 2 is a graph of the total amount of heat release of samples one, two, and three in example 1.
Detailed Description
The technical solution of the present invention is further described below with reference to examples.
Example 1
1. Preparation of flame-retardant heat-conducting agent
a) Preparation of sea urchin-shaped FeOOH: firstly, feSO with the concentration of 0.025M is added 4 ·7H 2 O is dispersed in a glycerol-water solution, wherein the solvent is glycerol: h 2 O volume ratio is 1:30, of a nitrogen-containing gas; then, the mixture was transferred to a 50mL hydrothermal reaction kettle and subjected to hydrothermal reaction at 110 ℃ for 24 hours. After 3 centrifugal washes with deionized water, a yellow powder was obtained after freeze drying.
b) Preparation (UF) of sea urchin-like ferroferric oxide: 1g of FeOOH and 2g of glucose are put into a mixed solvent of 15ml of ethanol and 35ml of deionized water for ultrasonic treatment. Then the mixture is transferred into a 50ml hydrothermal reaction kettle and undergoes a hydrothermal reaction for 12 hours at 180 ℃. And (4) centrifugal drying. The brown powder obtained was then calcined in a muffle furnace under nitrogen at a heating rate of 10 ℃ to 800 ℃ for 3h. Cooling to room temperature to obtain sea urchin-shaped Fe 3 O 4 。
c) Mixing 10g seaDispersing the gall-shaped ferroferric oxide in 150ml of ethanol, heating to 70 ℃, and stirring for 30min. Slowly dropwise adding 0.05mol of silane coupling agent (KH-550), and then slowly dropwise adding 10ml of H 2 And O. After 4 hours of reaction, 0.025mol of pyrophosphoric acid (PAA) was dissolved in 50ml of ethanol and slowly added dropwise to the solution, and the reaction was carried out for 2 hours. And then filtering and washing the product, and freeze-drying to obtain the flame-retardant heat-conducting agent.
d) The formula of the flame-retardant heat-conducting butadiene rubber composite material is shown in table 1.
TABLE 1 EXAMPLE 1 formulation of flame retardant thermally conductive butadiene rubber composite
The blending ratio of the sea urchin-shaped ferroferric oxide and the KH-550-pyrophosphoric acid in the sample III is obtained by calculating the load ratio of the flame-retardant heat-conducting agent.
Vulcanizing the mixed rubber for 20min at the temperature of 155 ℃ and the pressure of 5 MPa.
2. Performance testing
1. And (3) testing the flame retardant property: the micro calorimeter test is carried out according to the ASTM D7309-2007a standard, and a sample test is carried out by adopting a U.S. Govmark MCC-2 micro calorimeter, wherein the test temperature range is 100-600 ℃, and the sample mass is 5-8mg. The limiting oxygen index was measured by using HC-2C oxygen index meter (Jiangning analytical instruments, inc., china) according to the standard ASTM D2863. The size of the sample was 100X 10mm 3 。
2. And (3) testing the heat conductivity coefficient: the test was carried out according to GB 10297-98 standard using a TC3100 thermal conductivity meter (XianXixi, inc., china).
3. And (3) testing mechanical properties: the test was carried out according to GB/T6344-2008, the tensile rate of the specimen being 500mm/min.
4. And (3) testing results: table 2 shows the Limiting Oxygen Index (LOI), the peak heat release (phr), the total heat release value (THR), the thermal conductivity, and the tensile strength, elongation at break of the samples of the butadiene rubber composite. The general rubber flame-retardant heat-conducting agent prepared by the invention can effectively improve the flame-retardant property and the heat-conducting property of the butadiene rubber composite material.
TABLE 2 Performance test data for the butadiene rubber composite of example 1
The data in the table show that after the flame-retardant heat-conducting agent prepared by the scheme of the invention is added, the heat release peak value (PHRR) and the total heat release amount (THR) of the rubber composite material are greatly reduced, the oxygen index is obviously improved, the heat conductivity coefficient is also greatly improved, and the effect is still obvious compared with the blending of sea urchin-shaped ferric oxide and KH-550-pyrophosphoric acid, so that the flame-retardant heat-conducting agent prepared by the scheme of the invention can improve the flame-retardant and heat-conducting properties of the rubber composite material.
Example 2
1. Preparation of flame-retardant heat-conducting agent
a) Preparation of sea urchin-like FeOOH: firstly, 0.03M FeSO 4 ·7H 2 O dispersed in glycerol: h 2 The volume ratio of O is 1:40 in a solvent. Then, the mixture was transferred to a 50mL hydrothermal reaction kettle and subjected to hydrothermal reaction at 110 ℃ for 18 hours. After 3 centrifugal washes with deionized water, a yellow powder was obtained after freeze drying.
b) Preparation of echinoid ferroferric oxide (UF): 2g FeOOH and 2g glucose are put into a mixed solvent of 15ml ethanol and 35ml deionized water for ultrasonic treatment. Then the mixture is transferred into a 50ml hydrothermal reaction kettle and undergoes hydrothermal reaction for 24 hours at 180 ℃. And (4) centrifugal drying. The brown powder obtained is then calcined in a muffle furnace under nitrogen at a temperature rise rate of 10 ℃ to 700 ℃ for 4h. Cooling to room temperature to obtain sea urchin-shaped Fe 3 O 4 。
c) Dispersing 10g of sea urchin-shaped ferroferric oxide in 150ml of ethanol, heating to 70 ℃, and stirring for 30min. Slowly dropwise adding 0.1mol of silane coupling agent (KH-550), and then slowly dropwise adding 10ml of H 2 And O. After 4 hours of reaction, 0.05mol of pyrophosphoric acid (PAA) was dissolved in 50ml of ethanol and slowly added dropwise to the solution to react for 2 hours. And then filtering and washing the product, and freeze-drying to obtain the flame-retardant heat-conducting agent.
d) The formula of the flame-retardant heat-conducting styrene-butadiene rubber composite material is shown in table 3.
Table 3 example 2 formula of flame-retardant heat-conductive styrene butadiene rubber composite material
Vulcanizing the mixed rubber for 25min at 160 ℃ and 5 MPa.
2. Performance test
1. And (3) testing the flame retardant property: the micro calorimeter test is carried out according to the ASTM D7309-2007a standard, and a sample test is carried out by adopting a U.S. Govmark MCC-2 micro calorimeter, wherein the test temperature range is 100-600 ℃, and the sample mass is 5-8mg. The limiting oxygen index test was carried out according to the procedure and determination of ASTM D2863 using an HC-2C oxygen index apparatus (Jianning Analyzer, inc., china). The size of the sample was 100X 10mm 3 。
2. And (3) testing the heat conductivity coefficient: the test was carried out according to GB 10297-98 standard using a TC3100 thermal conductivity meter (XianXixi, inc., china).
3. And (3) testing results: table 4 shows the Limiting Oxygen Index (LOI), the peak value of heat release (pHRR), the total heat release value (THR), and the thermal conductivity of the styrene-butadiene rubber composite samples. The general rubber flame-retardant heat-conducting agent prepared by the invention can effectively improve the flame-retardant property and the heat-conducting property of the styrene butadiene rubber composite material.
Table 4 data of performance test of styrene butadiene rubber composite of example 2
Example 3
1. Preparation of flame-retardant heat-conducting agent
a) Preparation of sea urchin-shaped FeOOH: firstly, 0.035M FeSO 4 ·7H 2 O dispersed in glycerol: h 2 The volume ratio of O is 1:50 of solvent. Then, the mixture was transferred to a 50mL hydrothermal reaction kettle and subjected to hydrothermal reaction at 110 ℃ for 18 hours. After 3 times of centrifugal washing with deionized water, yellow powder was obtained after freeze drying.
b) Preparation (UF) of sea urchin-like ferroferric oxide: 3g of FeOOH and 2g of glucose are placed into a mixed solvent of 15ml of ethanol and 35ml of deionized water for ultrasonic treatment. Then the mixture is transferred into a 50ml hydrothermal reaction kettle and is subjected to hydrothermal reaction for 18h at 180 ℃. And (4) centrifugal drying. The brown powder obtained is then calcined in a muffle furnace with exclusion of oxygen at a heating rate of 10 ℃ to 900 ℃ for 2h. Cooling to room temperature to obtain sea urchin-shaped Fe 3 O 4 ；
c) Dispersing 10g of sea urchin-shaped ferroferric oxide in 150ml of ethanol, heating to 70 ℃, and stirring for 30min. Slowly dropwise adding 0.05mol of silane coupling agent (KH-550), and then slowly dropwise adding 10ml of H 2 And (O). After 4 hours of reaction, 0.05mol of pyrophosphoric acid (PAA) was dissolved in 50ml of ethanol and slowly added dropwise to the solution to react for 2 hours. And then filtering and washing the product, and freeze-drying to obtain the flame-retardant heat-conducting agent.
d) The formulation of the flame retardant, thermally conductive natural rubber composite is shown in table 5.
TABLE 5 EXAMPLE 3 formulation of flame retardant, thermally conductive Natural rubber composite
Vulcanizing the mixed rubber for 15min at 150 ℃ and 5 MPa.
2. Performance testing
1. And (3) testing the flame retardant property: the micro calorimeter test is carried out according to the ASTM D7309-2007a standard, and a sample test is carried out by adopting a U.S. Govmark MCC-2 micro calorimeter, wherein the test temperature range is 100-600 ℃, and the sample mass is 5-8mg. The limiting oxygen index test is carried out according to the standard ASTM D2863The measurement was carried out by using HC-2C oxygen index instrument (Jiangnin Analyzer, ltd., china). The size of the sample was 100X 10mm 3 。
2. And (3) testing the heat conductivity coefficient: the test was carried out according to GB 10297-98 standard using a TC3100 thermal conductivity meter (XianXixi, inc., china).
3. And (3) testing results: table 3 shows the Limiting Oxygen Index (LOI), the peak value of heat release (pHRR), the total heat release value (THR), and the thermal conductivity of the natural rubber composite samples. The general rubber flame-retardant heat-conducting agent prepared by the invention can effectively improve the flame-retardant property and the heat-conducting property of the styrene butadiene rubber composite material.
Table 6 example 3 performance test data for natural rubber composites
Claims (10)
1. A flame-retardant heat-conducting agent for general rubber is characterized in that: the flame-retardant heat-conducting agent is prepared by firstly preparing sea urchin-shaped ferroferric oxide by a hydrothermal method, then performing graft modification on the surface of the sea urchin-shaped ferroferric oxide by KH-550, and finally reacting the sea urchin-shaped ferroferric oxide with pyrophosphoric acid.
2. A method for preparing the flame-retardant and heat-conducting agent for general rubber as claimed in claim 1, comprising the steps of:
(a) Dispersing ferrous salt in a glycerol-water solution, and reacting for 12-24h in a hydrothermal reaction kettle at 110-150 ℃ to obtain sea urchin-shaped FeOOH;
(b) Dispersing sea urchin-shaped FeOOH and glucose in water, reacting for 12-24h in a hydrothermal reaction kettle at 160-200 ℃ to obtain reaction precipitate, and calcining the precipitate to obtain sea urchin-shaped ferroferric oxide;
(c) Dispersing sea urchin-shaped ferroferric oxide in ethanol, adding KH-550 at the temperature of 60-80 ℃, reacting for 3-5h, then adding pyrophosphoric acid, reacting for 1-3h, filtering, washing, precipitating and drying to obtain the flame-retardant heat-conducting agent for the general rubber.
3. The method for preparing a flame-retardant and heat-conductive agent for general rubber according to claim 2, wherein: in the step (a), the volume ratio of glycerol to water in the glycerol-water solution is 1:30-50.
4. The method for preparing a flame-retardant and heat-conductive agent for general rubber according to claim 2, wherein: in the step (a), the ferrous salt is ferrous sulfate, and the concentration of the ferrous salt is 0.025-0.035M.
5. The method for preparing a flame-retardant and heat-conductive agent for general rubber according to claim 2, wherein: in the step (b), the mass ratio of the sea urchin-shaped FeOOH to the glucose is (0.5-1.5 g): 1g of the total weight of the composition.
6. The method for preparing a flame-retardant heat-conducting agent for general rubber according to claim 2, characterized in that: in the step (b), the calcination is to react the precipitate with N 2 Calcining for 2-4h at 700-900 ℃ in the atmosphere to obtain the sea urchin-shaped ferroferric oxide.
7. The method for preparing a flame-retardant and heat-conductive agent for general rubber according to claim 2, wherein: in the step (c), the mass molar ratio of the sea urchin-shaped ferroferric oxide to the KH550 to the pyrophosphoric acid is 10g, i.e., 0.05 to 0.1mol and 0.025 to 0.05 mol.
8. The preparation method of the flame-retardant heat-conducting general rubber is characterized by comprising the following steps: the flame-retardant heat-conducting agent as defined in claim 1 or the flame-retardant heat-conducting agent prepared by the method as defined in claims 2-7, and other raw materials are prepared by mixing the following raw materials in parts by mass: 100 parts of general rubber, 5 parts of ZnO, 2 parts of stearic acid, 1.5-2.5 parts of vulcanization accelerator NS, 1.5-2.5 parts of anti-aging agent RD, 30-50 parts of carbon black, 1.5-2.5 parts of sulfur, 15-20 parts of diethyl aluminum phosphinate and 5-15 parts of flame-retardant heat-conducting agent.
9. The preparation method of the flame-retardant heat-conducting general rubber according to claim 8, characterized in that: the general rubber is at least one of butadiene rubber, styrene butadiene rubber and natural rubber.
10. The preparation method of the flame-retardant heat-conducting general rubber according to claim 8, characterized by comprising the following steps: the mixing method of the general rubber comprises the following steps: adding general rubber, zinc oxide, stearic acid, an anti-aging agent, an accelerator, carbon black, diethyl aluminum hypophosphite, a flame-retardant heat-conducting agent and sulfur into an internal mixer in sequence; after being mixed evenly, the mixture is pressed into tablets in an open mill, and vulcanized by a flat vulcanizing machine, wherein the vulcanizing pressure is 5MPa, the vulcanizing time is 10-30min, and the vulcanizing temperature is 150-170 ℃.
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